Organic water-soluble fertilizer containing humic acid and fulvic acid as well as preparation method and application of organic water-soluble fertilizer

Abstract

The invention belongs to the technical field of liquid fertilizers, and discloses an organic water-soluble fertilizer containing humic acid and fulvic acid as well as a preparation method and application of the organic water-soluble fertilizer. The organic water-soluble fertilizer comprises a composite humic acid matrix, urea, monoammonium phosphate, potassium nitrate, polyglutamic acid, triphenylsilanol, nano silicon, a composite microbial inoculant and disodium ethylene diamine tetraacetate by weight, wherein the composite humic acid matrix is prepared by mixing hydrothermal synergistic conversion humic acid and biochemical fulvic acid according to a ratio of (2-4): 1; the preparation method comprises the following steps: dissolving the basic components, chelating and synergistic, compounding and curing, and treating a finished product, wherein the curing temperature is controlled to be 35-40 DEG C in the compounding and curing stage. Short-term adjustment and long-term stability of soil pH can be considered, the flocculation resistance of a system and the survival rate of the microbial inoculum are improved, and when the microbial inoculum is applied to tomato and grape planting, obstacle soil conditions can be improved, crop growth indexes, stress resistance, yield and fruit quality can be improved, and the microbial inoculum is suitable for drought, saline-alkali and continuous cropping obstacle scenes.

Description

Technical Field

[0001] This invention belongs to the field of liquid fertilizer technology, and relates to an organic water-soluble fertilizer containing humic acid and fulvic acid, its preparation method and application. Background Technology

[0002] With the large-scale development of agricultural production and the widespread adoption of long-term continuous cropping, soil degradation problems have become increasingly prominent, such as soil acidification, salinization, decreased organic matter content, and microbial imbalance. These issues not only weaken the soil's water and fertilizer retention capacity but also easily trigger a chain reaction, including hindered crop root growth, reduced stress resistance, decreased yield, and deteriorated fruit quality, significantly restricting sustainable agricultural development. Against this backdrop, organic water-soluble fertilizers, with their dual functions of nutrient supply and soil conditioning, have gradually become an important technical means to improve the soil environment and enhance crop production efficiency. Among them, organic water-soluble fertilizers containing humic acid and fulvic acid have received widespread attention and application due to the advantages of humic acid substances in improving soil structure and promoting nutrient absorption.

[0003] However, current organic water-soluble fertilizers containing humic acid and fulvic acid still have many limitations: On the one hand, the sources of humic acid and fulvic acid in existing products are singular or the ratios are unreasonable, mostly relying on extraction and preparation from a single raw material, making it difficult to achieve synergistic effects in soil conditioning. This often manifests as rapid short-term soil pH adjustment but poor long-term stability, failing to meet the need for long-term soil improvement. Simultaneously, some products do not retain the activity of humic acid substances sufficiently, further weakening their role in increasing soil organic matter content and activating soil enzyme activity. On the other hand, the stability design of existing products has flaws. Most only use single chelation or colloidal stabilization technologies, which easily lead to flocculation and precipitation in hard water environments or high-concentration application scenarios, resulting in reduced fertilizer efficiency and clogging of irrigation systems. Furthermore, although some products add microbial agents to optimize soil flora, due to problems such as improper temperature control in the preparation process, the survival rate of live bacteria in the agents is low, making it difficult to fully exert their function of inhibiting harmful microorganisms and improving soil microecology.

[0004] Furthermore, existing organic water-soluble fertilizers are not specifically designed for special planting scenarios such as arid and saline-alkali areas or soils with continuous cropping obstacles. For example, in arid and saline-alkali areas, products often lack effective water-retaining components and salt-reducing mechanisms, failing to meet the needs of soil water and fertilizer retention as well as salinization improvement. In soils with continuous cropping obstacles, existing products cannot simultaneously solve multiple problems such as soil salinization and crop quality improvement, and their single function limits their application scope and actual effect.

[0005] In summary, the current technical shortcomings of organic water-soluble fertilizers containing humic acid and fulvic acid in areas such as the synergistic ratio of humic acid substances, system stability, retention of microbial activity, and adaptability to special environments have become key bottlenecks restricting their further promotion and application. Therefore, developing an organic water-soluble fertilizer that can achieve efficient synergy between humic acid and fulvic acid, excellent system stability, sufficient microbial activity, and the dual effects of soil improvement and crop yield enhancement in different challenging soil environments has significant practical importance and market value. Summary of the Invention

[0006] To address the problems of poor synergistic effects of humic acid substances, insufficient system stability, low microbial activity, and difficulty in applying to planting scenarios in obstacle soils, current organic water-soluble fertilizers offer improvements by optimizing the ratio of composite humic acid matrix, constructing a triple-stabilized system, and precisely controlling preparation process parameters. Specifically, this invention provides the following technical solution.

[0007] First, this invention provides an organic water-soluble fertilizer containing humic acid and fulvic acid, comprising, by weight: The ingredients are: 50-70 parts of compound humic acid matrix, 15-25 parts of urea, 10-14 parts of monoammonium phosphate, 12-18 parts of potassium nitrate, 5-9 parts of polyglutamic acid, 0.5-1.5 parts of triphenylsilanol, 1-3 parts of nano-silicon, 3-5 parts of compound bacterial agent, and 1-3 parts of disodium ethylenediaminetetraacetate. The composite humic acid matrix is ​​prepared by mixing hydrothermal synergistic conversion humic acid and biochemical fulvic acid in a weight ratio of 2-4:1. The compound microbial agent is composed of Bacillus subtilis and Trichoderma at a viable count ratio of 2:1, and the total viable count of the compound microbial agent is 1.8 × 10⁻⁶. 8 ~2.6×10 8 CFU / g; The particle size of the nano-silicon is 50~100nm.

[0008] Furthermore, in the above-mentioned organic water-soluble fertilizer, the hydrothermal synergistic conversion of humic acid is prepared by the following method: After crushing the corn stalks to a particle size of ≤5mm, mix them with sludge at a weight ratio of 1.2~1.8:1. Add deionized water to the mixture to adjust the solid-liquid ratio to 1:5~1:8, and stir to form a uniform slurry. The slurry was transferred to a sealed reactor, and a 0.08-0.12 mol / L HCl solution with the same volume as the deionized water in the slurry was added. After sealing, the temperature was raised to 170-190°C, and the mixture was stirred at 150-200 rpm and reacted at a constant temperature for 3-5 hours. Let the temperature naturally drop to 75-85℃. Add 1.8-2.2 mol / L NaOH solution slowly at a ratio of 2-3 mL NaOH solution per 100 g of carbonized slurry. Stir at 150 rpm and react at a constant temperature for 2-4 hours. The filtrate is filtered through a 200-300 mesh filter cloth and collected to obtain hydrothermal synergistic humic acid. The solid content of the hydrothermal synergistic humic acid is 15-20 wt%, and the pH is 7.0-8.0.

[0009] Furthermore, in the above-mentioned organic water-soluble fertilizer, the biochemical fulvic acid is prepared by the following method: After crushing the sugarcane bagasse to a particle size of ≤3mm, mix it with poultry and livestock manure at a weight ratio of 0.8~1.2:1. Add deionized water to adjust the initial moisture content of the mixture to 60~65%, stir evenly, and then transfer it to a fermentation tank. The number of viable bacteria inoculated was 0.8 × 10⁸ 7 ~1.2×10 7 The yeast inoculum is CFU / g, and the amount of yeast inoculum is 0.5~1% of the weight of the mixture. After sealing, the temperature is controlled at 30~34℃ for constant temperature fermentation for 68~76 hours. During the fermentation process, the mixture is stirred at 100rpm for 15 minutes every 24 hours. After fermentation, add deionized water to adjust the solid-liquid ratio to 1:8, stir to form a slurry, add 2 mol / L NaOH solution to adjust the pH to 10.0~10.5, heat to 85℃ and stir at 200~250 rpm for 1.5h; After naturally cooling to 30℃, add disodium ethylenediaminetetraacetate at 0.8% of the weight of the extract, stir at 150 rpm for 1 hour, centrifuge at 3500 rpm for 15 minutes, and collect the supernatant. Biochemical fulvic acid is obtained by adding deionized water or concentrating under reduced pressure at 50-60℃ to achieve a solid content of 12-18 wt%, a pH of 5.0-6.0, and a fulvic acid purity of 55-61% in the supernatant.

[0010] Furthermore, the organic water-soluble fertilizer, by weight, comprises: The mixture consists of 60 parts of compound humic acid matrix, 20 parts of urea, 12 parts of monoammonium phosphate, 15 parts of potassium nitrate, 7 parts of polyglutamic acid, 1 part of triphenylsilanol, 2 parts of nano-silicon, 4 parts of compound bacterial agent, and 2 parts of disodium ethylenediaminetetraacetate.

[0011] Secondly, the present invention provides a method for preparing the organic water-soluble fertilizer, comprising the following steps: 1) Dissolving basic components: Take urea, monoammonium phosphate, and potassium nitrate, add 30-50% of the total amount of liquid composite humic acid matrix, stir evenly, heat to 50-60℃, stir at 400-500 rpm for 15-21 minutes until urea, monoammonium phosphate, and potassium nitrate are completely dissolved, and cool naturally to 30-34℃. 2) Chelation and synergistic effect: Add disodium ethylenediaminetetraacetate to the solution obtained in step 1), stir for 4-6 min, then add polyglutamic acid, triphenylsilanol and nano-silicon in sequence, and stir at 380-420 rpm for 10-14 min to form a stable system; 3) Compounding and maturation: Add the remaining liquid compound humic acid matrix to the stable system, heat to 40~44℃ and stir for 28~32 min, inoculate with compound bacterial agent, and mature at 100~140 rpm for 1.5~2.5 h under constant temperature of 35~40℃. 4) Finished product processing: After maturation, cool naturally to room temperature, adjust the pH to 6.8-7.2 with 0.08-0.12 mol / L HCl or NaOH, and filter through a 180-220 μm sieve to obtain the finished organic water-soluble fertilizer.

[0012] Furthermore, in step 1) of the above method, the added liquid composite humic acid matrix accounts for 40% of its total volume, the heating temperature is 55°C, the stirring speed is 450 rpm, the stirring time is 18 min, and the temperature after natural cooling is 32°C.

[0013] Furthermore, in step 2) of the above method, the stirring time after adding disodium ethylenediaminetetraacetate is 5 min, and the stirring speed after adding polyglutamic acid, triphenylsilanol, and nano-silicon is 400 rpm and the stirring time is 12 min.

[0014] Furthermore, in step 3) of the above method, the temperature after heating is 42°C, the stirring time is 30 min, the maturation temperature is 38°C, the stirring speed during maturation is 120 rpm, and the maturation time is 2 h.

[0015] Furthermore, in step 4) of the above method, the adjusted pH is 7.0 and the sieve aperture is 200 μm.

[0016] Thirdly, the present invention seeks protection for the application of the organic water-soluble fertilizer in the cultivation of crops in obstacle soils, wherein the obstacle soils include acidic degraded soils, saline-alkali soils, or continuous cropping obstacle soils; and the crops include tomatoes or grapes.

[0017] Compared with existing technologies, the present invention, "An organic water-soluble fertilizer containing humic acid and fulvic acid, its preparation method and application," has the following beneficial effects: Firstly, by optimizing the ratio of composite humic acid matrix, the efficient synergistic transformation of humic acid and biochemical fulvic acid through hydrothermal conversion is achieved, taking into account both the short-term soil pH adjustment rate and long-term stability, effectively increasing soil organic matter content, and improving the conditions of acidic, degraded, salinized, and continuously cropped soils.

[0018] Secondly, a triple stabilization system is constructed, combining the chelation of disodium ethylenediaminetetraacetate, the colloidal stabilization of polyglutamic acid, and the anti-agglomeration effect of triphenylsilanol, to avoid flocculation and precipitation in hard water environments or when applied at high concentrations, ensuring system stability and improving leaf adhesion rate.

[0019] Third, precise control of preparation process parameters, especially the maturation temperature of 35~40℃, ensures a high survival rate of live bacteria in the compound microbial agent, helping to activate soil enzyme activity and optimize soil microbial community.

[0020] Fourth, when applied to crops such as tomatoes and grapes, it can significantly improve crop root vitality, growth indicators and stress resistance, increase yield and improve fruit quality. It is suitable for special planting scenarios such as drought, salinity, and continuous cropping obstacles, and its overall benefits are superior to similar products on the market. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0022] Unless otherwise specified, the test methods in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0023] Example 1 This embodiment describes the basic preparation method of the organic water-soluble fertilizer.

[0024] I. Experimental Objective Verify the rationality of the organic water-soluble fertilizer formula (compound humic acid matrix + synergistic component + nutrient balance component) and the feasibility of the basic process (compound humic acid preparation + basic liquid preparation + chelation synergism + compound maturation) described in this invention.

[0025] II. Test Methods (a) Raw material preparation Preparation of composite humic acid matrix: Hydrothermal co-conversion of humic acid: Corn stalks with a particle size ≤5mm were mixed with sludge at a weight ratio of 1.5:1. Deionized water was added to the mixture to adjust the solid-liquid ratio (mixture:deionized water) to 1:6 (weight ratio), and the mixture was stirred to form a uniform slurry. The slurry was transferred to a sealed reactor, and 0.1mol / L HCl solution was added (the volume of HCl solution was the same as the volume of deionized water in the slurry). After sealing the reactor, the temperature was raised to 180℃, and the mixture was stirred at 1800rpm and kept at a constant temperature for 4 hours. After hydrothermal carbonization, the temperature is naturally cooled to 80℃. NaOH solution is added slowly at a ratio of 2-3 mL of 2 mol / L NaOH solution per 100 g of carbonized slurry, while stirring (150 rpm). The reaction is carried out at a constant temperature for 3 hours to complete the humification. After the humification reaction is completed, the reaction material is filtered with a 200-mesh filter cloth to remove unreacted solid residues (such as coarse fibers and sludge impurities), and the filtrate is collected, which is the liquid hydrothermal co-conversion humic acid; the filtrate index is tested, with a solid content of 15wt% and a pH of 7.6.

[0026] Biochemical fulvic acid: Sugarcane bagasse is crushed to a particle size of ≤3mm, mixed with poultry and livestock manure at a weight ratio of 1:1, deionized water is added to adjust the initial moisture content of the mixture to 65%, and after stirring evenly, it is transferred to a fermentation tank; The number of viable bacteria added to the fermenter was 1.0 × 10⁶. 7 Add CFU / g of yeast inoculum (the amount of yeast inoculum is 0.8% of the weight of the mixed materials), seal the fermentation tank, control the temperature inside the tank at 32℃, and ferment at a constant temperature for 72 hours. During the fermentation process, stir at 100 rpm for 15 minutes every 24 hours to avoid anaerobic putrefaction of the material. After fermentation, deionized water was added to the fermentation material to adjust the solid-liquid ratio to 1:8. The mixture was stirred to form a slurry. 2 mol / L NaOH solution was slowly added to adjust the pH of the slurry to 10.0~10.5. The temperature was raised to 85℃ and stirred at a constant temperature for 1.5 hours. The stirring speed was controlled at 200 rpm to promote the full dissolution of fulvic acid. After the alkaline extraction was completed, the temperature was naturally cooled to 30℃. 0.8% disodium ethylenediaminetetraacetate (EDTA-2Na) was added to the extract and stirred at 150 rpm for 1 h. Then, the mixture was centrifuged at 3500 r / min for 15 min to remove the metal complex precipitate at the bottom and the supernatant was collected. The supernatant was tested, and the solid content was controlled at 12-18 wt% and pH 5.0-6.0 by adding deionized water or concentrating (concentrating under reduced pressure at 50-60℃). The purity of fulvic acid was tested to be 58%, which means it is liquid biochemical fulvic acid.

[0027] A composite humic acid matrix is ​​obtained by mixing hydrothermal synergistic conversion humic acid and biochemical fulvic acid at a weight ratio of 2.5:1 (i.e., 2500g of hydrothermal synergistic conversion humic acid and 1000g of biochemical fulvic acid).

[0028] Other raw materials: urea, monoammonium phosphate, potassium nitrate, polyglutamic acid, triphenylsilanol, nano-silicon (particle size 50~100nm), compound microbial agent (Bacillus subtilis and Trichoderma at a 2:1 live bacteria ratio, total live bacteria count 2.2×10⁻⁶). 8 CFU / g), disodium ethylenediaminetetraacetate.

[0029] (II) Formula Proportioning By weight, it includes: 600g of compound humic acid matrix (450g of hydrothermal synergistic conversion of humic acid, 150g of biochemical fulvic acid, weight ratio 3:1), 200g of urea, 120g of monoammonium phosphate, 150g of potassium nitrate, 70g of polyglutamic acid, 10g of triphenylsilanol, 20g of nano-silicon, 40g of compound bacterial agent, and 20g of disodium ethylenediaminetetraacetate.

[0030] (III) Preparation process 1) Dissolving basic components: Take urea, monoammonium phosphate, and potassium nitrate, add 30-50% of the total amount of liquid composite humic acid matrix, stir evenly, heat to 55℃, stir at 450rpm for 18min until urea, monoammonium phosphate, and potassium nitrate are completely dissolved, and cool naturally to 32℃. 2) Chelation and synergistic effect: Add disodium ethylenediaminetetraacetate to the solution obtained in step 1), stir for 5 min, then add polyglutamic acid, triphenylsilanol and nano-silicon in sequence, and stir at 400 rpm for 12 min to form a stable system. 3) Compounding and maturation: Add the remaining liquid compound humic acid matrix to the stable system, heat to 42℃ and stir for 30 min, inoculate with compound bacterial agent, and mature at 120 rpm for 2 h under constant temperature of 38℃. 4) Finished product processing: After maturation, the product is naturally cooled to room temperature, and the pH is adjusted to 7.0 with 0.1mol / L HCl or NaOH. The product is then filtered through a 200μm sieve to obtain the finished organic water-soluble fertilizer.

[0031] (iv) Performance testing Physicochemical indicators: detection of total humic acid content, fulvic acid content, total N+P2O5+K2O content and pH; Stability: After the finished product has been left to stand at room temperature for 6 months, observe whether precipitation or stratification occurs; prepare a 300 mg / L hard aqueous solution of calcium and magnesium ions (using CaCl2 and MgCl2). Preparation of 6H2O, Ca 2+ Mg 2+=2:1), dilute the finished product 500 times and add it to a hard water solution, then observe whether flocculation occurs; Soil conditioning effect: Select acidic degraded soil (initial pH 5.0, organic matter content 1.5wt%), at 20g / m³ 2 Dosage (apply 20g of the finished organic water-soluble fertilizer per square meter after diluting the finished product 600 times), test the soil pH and organic matter content after 30 days and compare the data with the data before application.

[0032] III. Test Results The performance test results are shown in Table 1.

[0033] Table 1. Performance test results of the basic embodiment

[0034] IV. Experimental Conclusions The standard formula and preparation process of this embodiment are feasible, the physicochemical indicators of the finished product meet the standards, the stability is excellent, and it has a significant conditioning effect on acidic degraded soil. It can be used as the basic scheme for subsequent optimization and application embodiments. At the same time, through the composite humic acid matrix and multi-component synergistic design, this invention has significant effects in terms of nutrient supply, stability and soil conditioning, providing an effective technical basis for soil improvement and crop planting.

[0035] Comparative Example 2 This embodiment describes the effect of adjusting the ratio of compound humic acid.

[0036] I. Experimental Objective The study aimed to verify the effects of different weight ratios of hydrothermal synergistic conversion of humic acid and biochemical fulvic acid in the composite humic acid matrix on the stability of the organic water-soluble fertilizer, its short-term soil pH regulation effect, and its long-term soil pH retention capacity, and to determine the optimal ratio range.

[0037] II. Test Methods (a) Raw material preparation The preparation method of hydrothermal synergistic conversion of humic acid and biochemical fulvic acid is the same as in Example 1; other raw materials (polyglutamic acid, triphenylsilanol, nano-silicon, etc.) are the same as in Example 1.

[0038] (II) Formula Proportioning By weight, it includes: 600g of composite humic acid matrix (350g of hydrothermal synergistic conversion of humic acid + 250g of biochemical fulvic acid, weight ratio 1.4:1), 200g of urea, 120g of monoammonium phosphate, 150g of potassium nitrate, 70g of polyglutamic acid, 10g of triphenylsilanol, 20g of nano-silicon, 40g of composite microbial agent, and 20g of disodium ethylenediaminetetraacetate; the specifications and amounts of the remaining raw materials are completely consistent with those in Example 1.

[0039] (III) Preparation process The preparation steps (dissolving the basic components, chelating and enhancing, compounding and maturation, and finished product processing) and various process parameters (temperature, stirring speed, time, etc.) are the same as in Example 1.

[0040] (iv) Performance testing Stability testing: Same as in Example 1, observe the appearance (sedimentation, stratification) of the finished product after standing at room temperature for 6 months, and the flocculation in a 300 mg / L calcium and magnesium ion hard aqueous solution; Soil conditioning effect test: The same acidic degraded soil as in Example 1 (initial pH 5.0, organic matter content 1.5wt%) was selected, and soil conditioning effect was tested at 20g / m³. 2 Dosage: The finished organic water-soluble fertilizer was diluted 600 times and applied by drip irrigation. Soil pH was tested 30 days (short-term) and 60 days (long-term) after application, and the results were compared with those of Example 1.

[0041] III. Test Results The performance test results are shown in Table 2.

[0042] Table 2. Results of the experiment on the optimization of the ratio of compound humic acid

[0043] IV. Experimental Conclusions When the weight ratio of hydrothermal synergistic conversion of humic acid to biochemical fulvic acid is 1.4:1, the product stability still meets the standards, but the soil conditioning effect exhibits rapid short-term onset but poor long-term stability. This indicates that although this ratio can meet the short-term soil pH adjustment needs, it cannot achieve long-term stable acid control, failing to meet the requirements of high-standard farmland for long-term soil improvement. Comparative Example 1 (ratio 2.5:1) shows that when the weight ratio of hydrothermal synergistic conversion of humic acid to biochemical fulvic acid is in the range of 2~4:1, it can balance short-term conditioning speed and long-term stability, overcoming the limitations of conventional existing technologies that have short-term onset but insufficient long-term effects.

[0044] In summary, the optimal weight ratio of hydrothermal synergistic conversion of humic acid to biochemical fulvic acid in the composite humic acid matrix is ​​2:1 to 3:1. This ratio range is key to achieving rapid short-term neutralization and stable long-term regulation of soil pH.

[0045] Comparative Example 3 This embodiment describes the effect of adjusting the synergistic components.

[0046] I. Experimental Objective The effects of triphenylsilanol in the synergistic system on the anti-flocculation ability, high-concentration stability and leaf adhesion rate of the organic water-soluble fertilizer were verified, and its role in the triple stabilization system of disodium ethylenediaminetetraacetate, polyglutamic acid and triphenylsilanol was clarified.

[0047] II. Test Methods (a) Raw material preparation Except for the removal of triphenylsilanol, the preparation methods, specifications and sources of the other raw materials (composite humic acid matrix, polyglutamic acid, nano-silicon, composite bacterial agent, etc.) are the same as in Example 1.

[0048] (II) Formula Proportioning Only triphenylsilanol was removed from Example 1, while the amounts of the remaining raw materials were exactly the same as in Example 1.

[0049] (III) Preparation process The preparation steps (dissolving the basic components, chelating and enhancing, compounding and maturation, and finished product processing) and various process parameters (temperature, stirring speed, time, etc.) are the same as in Example 1.

[0050] (iv) Performance testing Anti-flocculation ability test: Prepare a 300 mg / L calcium and magnesium ion hard water solution, dilute the finished product by 300 times (high concentration), 500 times (normal concentration), and 800 times (low concentration), respectively, add it to the hard water solution, let it stand for 30 minutes, observe the flocculation and calculate the sedimentation rate; High concentration stability test: The finished product is left to stand at room temperature. Samples are taken every 3 months to test the appearance (precipitation, stratification). At 6 months, the amount of humic acid precipitation is tested: According to NY / T 1971-2010 "Determination of Humic Acid Content in Water-Soluble Fertilizers", 100 mL of the finished product solution is taken, centrifuged at 4000 r / min for 30 min, the precipitate is collected and dried to constant weight, and the amount of humic acid precipitation is calculated as follows: precipitation amount = mass of humic acid in precipitate / total mass of humic acid in solution × 100%; Leaf adhesion rate test: Select healthy corn leaves of the same variety, at the same growth stage, with consistent growth and free from pests and diseases, ensuring that the leaves are similar in size and integrity. Rinse with deionized water and air dry. Dilute the fertilizer solution of this example and the fertilizer solution of Example 1 by 800 times. Weigh the initial weight (m1) of each leaf. Under windless and room temperature conditions, spray the fertilizer solution at a fixed distance between the nozzle and the leaf to ensure consistent spraying amount. After standing for 10 minutes, weigh the total weight of the leaves after spraying (m2). Weight of fertilizer solution attached to a single leaf = m2 - m1; Leaf adhesion rate = (weight of fertilizer solution attached to a single leaf × number of leaves) / total weight of fertilizer solution sprayed × 100%. Each group was tested in triplicate, and the average value was taken. At the same time, a control group of Example 1 with the same amount of fertilizer solution was set up.

[0051] III. Test Results The performance test results are shown in Table 3.

[0052] Table 3. Results of Synergistic Optimization Experiment of Synergistic Components

[0053] IV. Experimental Conclusions After removing triphenylsilanol, the product's anti-flocculation ability, high-concentration stability, and leaf adhesion rate all decreased significantly. It showed obvious defects, especially in high-concentration application scenarios (such as the initial stage of drip irrigation). This proves that triphenylsilanol is a key component in maintaining the triple stability system. It can enhance the system's resistance to hard water and high-concentration precipitation by reducing the surface tension of fertilizer solution and inhibiting the aggregation of humic acid molecules.

[0054] Comparative Example 4 This example describes the effect of temperature adjustment in the preparation process.

[0055] I. Experimental Objective The study aimed to verify the effect of temperature during the maturation stage of the compound microbial agent on the survival rate of viable microorganisms and the activation effect on soil enzyme activity, and to determine the optimal range of maturation temperature.

[0056] II. Test Methods (a) Raw material preparation The preparation methods, specifications, and sources of all raw materials (composite humic acid matrix, polyglutamic acid, triphenylsilyl alcohol, composite microbial agent, etc.) are consistent with those in Example 1. The composite microbial agent is a mixture of Bacillus subtilis and Trichoderma at a viable cell ratio of 2:1, with an initial viable cell count of 2.2 × 10⁻⁶. 8 CFU / g.

[0057] (II) Formula Proportioning Completely consistent with Example 1.

[0058] (III) Preparation process Only the maturation temperature of the compounding and maturation stage was adjusted to 30°C. All other steps (dissolving the basic components, chelating and enhancing, and processing the finished product) and process parameters (stirring speed, time, pH adjustment, etc.) were the same as in Example 1.

[0059] (iv) Performance testing Viable count of compound microbial agent: After maturation, the viable count of compound microbial agent in the finished product is detected by dilution plate counting method, and the survival rate is calculated as follows: survival rate = viable count after maturation / initial viable count × 100%; Soil enzyme activity detection: The same acidic degraded soil as in Example 1 was selected, and the enzyme activity was measured at 20 g / m³. 2 Dosage: Dilute the finished organic water-soluble fertilizer 600 times and apply by drip irrigation; 30 days later, the activity of soil urease was detected by sodium phenolate-sodium hypochlorite colorimetric method; the activity of dehydrogenase was detected by TTC colorimetric method. At the same time, a control group of Example 1 and a blank control group (only water was applied) were set up.

[0060] III. Test Results The performance test results are shown in Table 4.

[0061] Table 4. Results of temperature optimization experiments in the preparation process

[0062] IV. Experimental Conclusions When the maturation temperature drops to 30℃, the survival rate of the compound microbial agent decreases significantly, and the reproduction of Bacillus subtilis and Trichoderma is inhibited, leading to a reduction in the number of beneficial microorganisms in the soil. This, in turn, weakens the activation effect of soil enzymes, proving that low-temperature maturation cannot simultaneously ensure the survival of the microbial agent and the activity of humic acid, thus failing to meet the functional requirements of the product. As shown in Example 1 (maturation at 38℃), a maturation temperature of 35~40℃ can achieve the optimal effect through the following mechanisms: First, it meets the compatibility requirements of Bacillus subtilis (optimal growth temperature 35~40℃) and Trichoderma (optimal growth temperature 30~35℃), ensuring the survival rate of live bacteria; second, it avoids the decomposition of humic acid functional groups (carboxyl groups, phenolic hydroxyl groups) caused by high temperatures (>45℃), maintaining its soil conditioning activity.

[0063] Example 5 This embodiment describes the application of the organic water-soluble fertilizer in tomato cultivation in soil with continuous cropping obstacles.

[0064] I. Experimental Objective This study aims to verify the effects of the organic water-soluble fertilizer provided by this invention on improving tomato growth, stress resistance, yield, and fruit quality in tomato cultivation in Changji area of ​​Xinjiang (arid, mildly saline-alkali soil, and continuous cropping obstacles), and to explore the applicability of the technical solution of this invention to tomato cultivation in soil with continuous cropping obstacles.

[0065] II. Test Methods (a) Test materials Test fertilizers: organic water-soluble fertilizer prepared according to the formula and process of Example 1; commercially available organic water-soluble fertilizer (Jinan Shengshi Chuangfu Chemical Co., Ltd.).

[0066] Test soil: Tomato planting soil in Changji Prefecture, Xinjiang, which had been continuously cropped for 6 years. The initial pH was 8.1, EC value was 3.2 mS / cm, and organic matter content was 0.9 wt%. The continuous cropping obstacles were manifested as soil salinization, microbial community imbalance, and root growth inhibition.

[0067] The test crop was the tomato variety "Jinpeng No. 1". Healthy seedlings with a seedling age of 35 days, a plant height of about 15cm, and uniform growth were selected.

[0068] (II) Experimental Design The experiment consisted of three treatment groups, with three replicates per group, and each plot was 20m². 2 (Tomato transplanting density 2 plants / m²) 2 (5 plants per row, 4 rows in total), randomly arranged in blocks, with consistent field management (drip irrigation, pruning, and basic pest and disease control) across all blocks: Experimental group: The product of this embodiment was applied using a combination of drip irrigation and root drenching. The drip irrigation solution was diluted 750 times (once each time on days 10, 25, and 40 after transplanting, with a dilution volume of 2 kg / m² each time). 2 Dilute 500 times for root irrigation (once on the 15th and 30th day after transplanting, 0.5L per plant). Control group: Commercially available organic water-soluble fertilizer products were applied, with the same application method, dilution ratio, dosage, and time as the experimental group; Control group: Only drip irrigation and root irrigation with the same amount of clean water were used, without fertilizer application.

[0069] (III) Detection Indicators and Methods Growth indicators: During the tomato fruit expansion period (45 days after transplanting), 10 plants were randomly selected from each plot. Root activity was tested using the TTC method (measured as μg of TTC reduced per gram of fresh root per hour), and plant height (from ground surface to plant top) was measured. Resistance index: Mortality rate (number of dead plants / total number of plants) at harvest time (120 days after transplanting) × 100%. Yield targets: Harvest all tomato fruits in the plot, weigh and calculate the total yield of the plot, and convert it to the theoretical yield per mu (based on 667m²). 2 (Conversion); Count the number of fruits per plant of 10 tomato plants in each plot, randomly select 30 fruits, weigh the weight of each fruit, and take the average value; Quality indicators: Thirty fruits were randomly selected, and the soluble sugar content was determined by Fehling's reagent titration method; the vitamin C content was determined by high performance liquid chromatography. Soil indicators: After harvest, soil samples were taken at a depth of 20cm to test the soil pH and EC values.

[0070] III. Test Results The performance test results are shown in Table 5.

[0071] Table 5. Results of the tomato planting experiment

[0072] IV. Experimental Conclusions The organic water-soluble fertilizer provided by this invention can significantly improve tomato root vitality and plant height, reduce plant mortality, and increase yield per acre in tomato cultivation in soil with continuous cropping obstacles in facility agriculture. At the same time, it can increase the soluble sugar content of the fruit and improve soil salinization and other problems. Its effect is better than that of commercially available organic water-soluble fertilizers, proving that it has a good application effect on tomato cultivation in soil with continuous cropping obstacles.

[0073] Comparative analysis revealed that commercially available organic water-soluble fertilizers failed to address issues related to soil salinity reduction, disease control, and quality improvement during continuous cropping. In contrast, this invention, through a design combining a compound humic acid matrix, compound microbial agents, and triphenylsilanol, can reduce soil EC values ​​and optimize soil microbial communities and enhance fruit sugar accumulation through the compound microbial agents, thus overcoming the shortcomings of existing water-soluble fertilizers with limited functionality.

[0074] In summary, the organic water-soluble fertilizer provided by this invention is suitable for tomato cultivation in obstacle soils.

[0075] Example 6 This embodiment describes the application of the organic water-soluble fertilizer in grape cultivation.

[0076] I. Experimental Objective The study aims to verify the effects of the described organic water-soluble fertilizer on grape growth, yield, and fruit quality in grape cultivation in the Turpan region of Xinjiang (arid, saline-alkali soil, and lack of organic matter), and to clarify the applicability of the technical solution of this invention to grape cultivation in Xinjiang.

[0077] II. Test Methods (a) Test materials Test fertilizers: organic water-soluble fertilizer prepared according to the formula and process of Example 1; commercially available organic water-soluble fertilizer (Jinan Shengshi Chuangfu Chemical Co., Ltd.).

[0078] The tested soil was from a vineyard in Turpan, Xinjiang. The initial pH was 8.3, the EC value was 3.5 mS / cm, the organic matter content was 1.1 wt%, the available phosphorus was 8 mg / kg, and the available potassium was 95 mg / kg. The soil characteristics were drought, poor water and fertilizer retention capacity, and slight salinization.

[0079] The test crop was the grape variety “Seedless White”, and healthy vines of 5 years old with uniform vigor were selected.

[0080] (II) Experimental Design The experiment consisted of three treatment groups, with three replicates per group, and the plot area was 40m². 2 (10 grapevines per plot, 2m x 2m spacing), randomly arranged in blocks, with consistent field management (irrigation, pruning, and pest and disease control) across all blocks. Drip irrigation is used for irrigation. Experimental group: The organic water-soluble fertilizer of this invention was applied via drip irrigation, diluted 800 times, and applied once each during the grape budding stage (late March), 10 days before flowering (mid-April), and the fruit expansion stage (late May). The dosage of the diluted solution was 2 kg / m² each time. 2 ; Control group: Commercially available organic water-soluble fertilizer products were applied, with the same application method, dilution ratio, dosage, and time as the experimental group; Blank group: Only drip irrigation with the same amount of clean water, without fertilizer application.

[0081] (III) Detection Indicators and Methods Growth indicators: 10 days before grape flowering (mid-April), 10 new shoots were randomly selected from each plot and their length was measured; during the fruit ripening period (late July), 5 grapevines were randomly selected from each plot, and the number of fruiting branches per vine and the total number of branches were counted. The fruiting branch rate per vine was calculated, and the average of the 5 vines was taken as the fruiting branch rate of the plot. Yield targets: Harvest all grapes in the plot, weigh and calculate the total yield of the plot, and convert it to the average yield per mu (based on 667m²). 2 (conversion) Quality indicators: Thirty fruits were randomly selected, and the soluble solids content was determined by refractometer method; the titratable acid content was determined by titration method, and the sugar-acid ratio (soluble solids content / titratable acid content) was calculated. Soil indicators: After harvest, soil samples were taken to test soil pH, EC value and organic matter content, and compared with the initial values.

[0082] III. Test Results The performance test results are shown in Table 6.

[0083] Table 6. Results of the grape cultivation trial

[0084] IV. Experimental Conclusions The product of this embodiment can significantly promote the growth of new grape shoots, increase the fruiting branch rate, and increase the yield per acre in grape cultivation in Xinjiang. At the same time, it can improve the soluble solids content and sugar-acid ratio of the fruit, and improve the soil salinization and organic matter level. The effect is better than that of commercially available organic water-soluble fertilizers, proving its good applicability to grape cultivation in the arid and saline-alkali areas of Xinjiang.

[0085] Comparative analysis revealed that commercially available organic water-soluble fertilizers failed to address the issues of water and fertilizer retention, salinity regulation, and quality improvement in Xinjiang. This solution, however, utilizes a synergistic design of a composite humic acid matrix, polyglutamic acid, and nano-silicon. Polyglutamic acid enhances soil water retention, making it suitable for the arid environment of Xinjiang; nano-silicon and humic acid work together to reduce soil EC values; and the composite humic acid increases organic matter and promotes nutrient absorption, overcoming the functional limitations of existing water-soluble fertilizers in arid and saline-alkali regions.

[0086] In summary, the organic water-soluble fertilizer described in this invention is suitable for grape cultivation in Xinjiang and similar arid and saline-alkali regions.

[0087] The embodiments described above are only some, not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art through related deductions and substitutions based on the inventive concept, without inventive effort, are within the scope of protection of the present invention.

Claims

1. An organic water-soluble fertilizer containing humic acid and fulvic acid, characterized in that, By weight, it includes: The ingredients are: 50-70 parts of compound humic acid matrix, 15-25 parts of urea, 10-14 parts of monoammonium phosphate, 12-18 parts of potassium nitrate, 5-9 parts of polyglutamic acid, 0.5-1.5 parts of triphenylsilanol, 1-3 parts of nano-silicon, 3-5 parts of compound bacterial agent, and 1-3 parts of disodium ethylenediaminetetraacetate. The composite humic acid matrix is ​​prepared by mixing hydrothermal synergistic conversion humic acid and biochemical fulvic acid in a weight ratio of 2-4:

1. The compound microbial agent is composed of Bacillus subtilis and Trichoderma at a viable count ratio of 2:1, and the total viable count of the compound microbial agent is 1.8 × 10⁻⁶. 8 ~2.6×10 8 CFU / g; The particle size of the nano-silicon is 50~100nm.

2. The organic water-soluble fertilizer according to claim 1, characterized in that, The hydrothermal synergistic conversion of humic acid is prepared by the following method: After crushing the corn stalks to a particle size of ≤5mm, mix them with sludge at a weight ratio of 1.2~1.8:

1. Add deionized water to the mixture to adjust the solid-liquid ratio to 1:5~1:8, and stir to form a uniform slurry. The slurry was transferred to a sealed reactor, and a 0.08-0.12 mol / L HCl solution with the same volume as the deionized water in the slurry was added. After sealing, the temperature was raised to 170-190°C, and the mixture was stirred at 150-200 rpm and reacted at a constant temperature for 3-5 hours. Let the temperature naturally drop to 75-85℃. Add 1.8-2.2 mol / L NaOH solution slowly at a ratio of 2-3 mL NaOH solution per 100 g of carbonized slurry. Stir at 150 rpm and react at a constant temperature for 2-4 hours. The filtrate is filtered through a 200-300 mesh filter cloth and collected to obtain hydrothermal synergistic humic acid. The solid content of the hydrothermal synergistic humic acid is 15-20 wt%, and the pH is 7.0-8.

0.

3. The organic water-soluble fertilizer according to claim 1, characterized in that, The biochemical fulvic acid is prepared by the following method: After crushing the sugarcane bagasse to a particle size of ≤3mm, mix it with poultry and livestock manure at a weight ratio of 0.8~1.2:

1. Add deionized water to adjust the initial moisture content of the mixture to 60~65%, stir evenly, and then transfer it to a fermentation tank. The number of viable bacteria inoculated was 0.8 × 10⁸ 7 ~1.2×10 7 The yeast inoculum is CFU / g, and the amount of yeast inoculum is 0.5~1% of the weight of the mixture. After sealing, the temperature is controlled at 30~34℃ for constant temperature fermentation for 68~76 hours. During the fermentation process, the mixture is stirred at 100rpm for 15 minutes every 24 hours. After fermentation, add deionized water to adjust the solid-liquid ratio to 1:8, stir to form a slurry, add 2 mol / L NaOH solution to adjust the pH to 10.0~10.5, heat to 85℃ and stir at 200~250 rpm for 1.5h; After naturally cooling to 30℃, add disodium ethylenediaminetetraacetate at 0.8% of the weight of the extract, stir at 150 rpm for 1 hour, centrifuge at 3500 rpm for 15 minutes, and collect the supernatant. Biochemical fulvic acid is obtained by adding deionized water or concentrating under reduced pressure at 50-60℃ to achieve a solid content of 12-18 wt%, a pH of 5.0-6.0, and a fulvic acid purity of 55-61% in the supernatant.

4. The organic water-soluble fertilizer according to claim 1, characterized in that, By weight, it includes: The mixture consists of 60 parts of compound humic acid matrix, 20 parts of urea, 12 parts of monoammonium phosphate, 15 parts of potassium nitrate, 7 parts of polyglutamic acid, 1 part of triphenylsilanol, 2 parts of nano-silicon, 4 parts of compound bacterial agent, and 2 parts of disodium ethylenediaminetetraacetate.

5. The method for preparing the organic water-soluble fertilizer according to any one of claims 1 to 4, characterized in that, Includes the following steps: 1) Dissolving basic components: Take urea, monoammonium phosphate, and potassium nitrate, add 30-50% of the total amount of liquid composite humic acid matrix, stir evenly, heat to 50-60℃, stir at 400-500 rpm for 15-21 minutes until urea, monoammonium phosphate, and potassium nitrate are completely dissolved, and cool naturally to 30-34℃. 2) Chelation and synergistic effect: Add disodium ethylenediaminetetraacetate to the solution obtained in step 1), stir for 4-6 min, then add polyglutamic acid, triphenylsilanol and nano-silicon in sequence, and stir at 380-420 rpm for 10-14 min to form a stable system; 3) Compounding and maturation: Add the remaining liquid compound humic acid matrix to the stable system, heat to 40~44℃ and stir for 28~32 min, inoculate with compound bacterial agent, and mature at 100~140 rpm for 1.5~2.5 h under constant temperature of 35~40℃. 4) Finished product processing: After maturation, cool naturally to room temperature, adjust the pH to 6.8-7.2 with 0.08-0.12 mol / L HCl or NaOH, and filter through a 180-220 μm sieve to obtain the finished organic water-soluble fertilizer.

6. The preparation method according to claim 5, characterized in that, In step 1), the added liquid composite humic acid matrix accounts for 40% of its total volume, the heating temperature is 55℃, the stirring speed is 450rpm, the stirring time is 18min, and the temperature after natural cooling is 32℃.

7. The preparation method according to claim 5, characterized in that, In step 2), the stirring time after adding disodium ethylenediaminetetraacetate is 5 min, and the stirring speed after adding polyglutamic acid, triphenylsilanol, and nano-silicon is 400 rpm and the stirring time is 12 min.

8. The preparation method according to claim 5, characterized in that, In step 3), the temperature after heating is 42℃, the stirring time is 30min, the maturation temperature is 38℃, the stirring speed during maturation is 120rpm, and the maturation time is 2h.

9. The preparation method according to claim 5, characterized in that, In step 4), the adjusted pH is 7.0 and the sieve aperture is 200μm.

10. The application of the organic water-soluble fertilizer according to any one of claims 1 to 4 in the cultivation of crops on obstacle soil, characterized in that, The obstacle soil includes acidic degraded soil, saline-alkali soil, or continuous cropping obstacle soil; the crop includes tomato or grape.

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